Synthetic inorganic chemistry
<p>This thesis is divided into two parts. The first part concerns the synthesis and characterisation of substituted metallocene complexes of the transition and main group metals. The second part describes the preparation and characterisation of inorganic fullerene (IF)-related materials.</...
| Main Authors: | , |
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| Format: | Thesis |
| Language: | English |
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2000
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| Subjects: |
| _version_ | 1797084674047082496 |
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| author | Clancy, G Clancy, Gerald Patrick |
| author2 | Green, M |
| author_facet | Green, M Clancy, G Clancy, Gerald Patrick |
| author_sort | Clancy, G |
| collection | OXFORD |
| description | <p>This thesis is divided into two parts. The first part concerns the synthesis and characterisation of substituted metallocene complexes of the transition and main group metals. The second part describes the preparation and characterisation of inorganic fullerene (IF)-related materials.</p> <p><strong>Chapter 1</strong> reviews the chemistry of dialkyl- and diaryl-phosphino substituted cyclopentadienyl complexes of the transition metals.</p> <p><strong>Chapter 2</strong> describes the synthesis and characterisation of the new ligands [M(C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>] (M = H, Li, Na and K) via the precursors [HC<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PHMe<sub>2</sub>][X] (X = Cl and PF<sub>6</sub>). The synthesis, characterisation and chemical reactivity of the compounds [Zr{{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub> and [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] is reported together with supporting evidence for the synthesis of the bimetallic complex [Zr{U+03B7-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub>PtI<sub>2</sub>] and the complex [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>]. <p><strong>Chapter 3</strong> provides a brief introduction into the field of main group metallocenes and describes the synthesis and characterisation of the new main group metallocenes [M{η- C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] (M = Pb and Sn). The B(C<sub>6</sub>F<sub>5</sub>)<sub>3 adduct [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>(B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>] has also been synthesised. The main group - transition metal bimetallic complex [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>PtI<sub>2<sub> in which the substitutedplumbocene acts as a bidentate ligand, has been characterised by mass spectrometry and <sup>31</sup>P{<sup>1</sup>H}NMR spectroscopy.</sub></sub></sub></p> <p><strong>Chapter 4</strong> provides an introduction into the field of IF-related materials and an overview of the analytical techniques used in their characterisation.</p> <p><strong>Chapter 5</strong> describes the preparation and characterisation of IF-MoS<sub>2</sub> and IF-(Nb,W)S<sub>2</sub> materials from MoC and the binary oxides Nb<sub>8</sub> W<sub>9</sub>O<sub>47</sub> and Nb<sub>4</sub>W<sub>13</sub>O<sub>47</sub> respectively. A powder X-ray diffraction study of the conversion of WC to WO<sub>3-X</sub> and the subsequent sulfidisation by H<sub>2</sub>S to form novel IF-WS<sub>2</sub> morphologies is also described.</p> <p><strong>Chapter 6</strong> describes the preparation of amorphous Group 5 metal (V, Nb and Ta) oxides using the metal vapour synthesis technique. These amorphous precursors have been annealed in a reducing atmosphere to form the oxide phases U+03B1-V<sub>2</sub>O<sub>3</sub>, NbO<sub>2</sub> and TT-Ta<sub>2</sub>O<sub>5</sub> which have been identified by powder X-ray diffraction. Upon reaction with H<sub>2</sub>S, the crystalline oxides afford layered sulfides of the form MS<sub>2</sub> (M = V, Nb and Ta), some of which exhibit behaviour typical of IF-like materials and have been characterised by HRTEM, powder X-ray diffraction and EDX analysis.</p> Chapter 7 outlines the experimental details for the synthesis, characterisation, reactions and compounds described in the preceding chapters. <p><strong>Chapter 8</strong> presents the characterising data for the new compounds described in chapters 2 and 3.</p> <p><strong>Appendix A</strong> contains details of the crystallographic data for the structurally characterised compound [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>PMe<sub>2</sub>}<sub>2</sub>].</sub></p></p> |
| first_indexed | 2024-03-07T01:58:19Z |
| format | Thesis |
| id | oxford-uuid:9c7f7c35-bb8f-4117-8e2e-e56a9fbcbeab |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:58:19Z |
| publishDate | 2000 |
| record_format | dspace |
| spelling | oxford-uuid:9c7f7c35-bb8f-4117-8e2e-e56a9fbcbeab2022-03-27T00:36:21ZSynthetic inorganic chemistryThesishttp://purl.org/coar/resource_type/c_db06uuid:9c7f7c35-bb8f-4117-8e2e-e56a9fbcbeabMolybdenum oxidesSynthesisDerivativesCyclopentadieneEnglishPolonsky Theses Digitisation Project2000Clancy, GClancy, Gerald PatrickGreen, MGreen, M<p>This thesis is divided into two parts. The first part concerns the synthesis and characterisation of substituted metallocene complexes of the transition and main group metals. The second part describes the preparation and characterisation of inorganic fullerene (IF)-related materials.</p> <p><strong>Chapter 1</strong> reviews the chemistry of dialkyl- and diaryl-phosphino substituted cyclopentadienyl complexes of the transition metals.</p> <p><strong>Chapter 2</strong> describes the synthesis and characterisation of the new ligands [M(C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>] (M = H, Li, Na and K) via the precursors [HC<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PHMe<sub>2</sub>][X] (X = Cl and PF<sub>6</sub>). The synthesis, characterisation and chemical reactivity of the compounds [Zr{{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub> and [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] is reported together with supporting evidence for the synthesis of the bimetallic complex [Zr{U+03B7-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub>PtI<sub>2</sub>] and the complex [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>]. <p><strong>Chapter 3</strong> provides a brief introduction into the field of main group metallocenes and describes the synthesis and characterisation of the new main group metallocenes [M{η- C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] (M = Pb and Sn). The B(C<sub>6</sub>F<sub>5</sub>)<sub>3 adduct [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>(B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>] has also been synthesised. The main group - transition metal bimetallic complex [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>PtI<sub>2<sub> in which the substitutedplumbocene acts as a bidentate ligand, has been characterised by mass spectrometry and <sup>31</sup>P{<sup>1</sup>H}NMR spectroscopy.</sub></sub></sub></p> <p><strong>Chapter 4</strong> provides an introduction into the field of IF-related materials and an overview of the analytical techniques used in their characterisation.</p> <p><strong>Chapter 5</strong> describes the preparation and characterisation of IF-MoS<sub>2</sub> and IF-(Nb,W)S<sub>2</sub> materials from MoC and the binary oxides Nb<sub>8</sub> W<sub>9</sub>O<sub>47</sub> and Nb<sub>4</sub>W<sub>13</sub>O<sub>47</sub> respectively. A powder X-ray diffraction study of the conversion of WC to WO<sub>3-X</sub> and the subsequent sulfidisation by H<sub>2</sub>S to form novel IF-WS<sub>2</sub> morphologies is also described.</p> <p><strong>Chapter 6</strong> describes the preparation of amorphous Group 5 metal (V, Nb and Ta) oxides using the metal vapour synthesis technique. These amorphous precursors have been annealed in a reducing atmosphere to form the oxide phases U+03B1-V<sub>2</sub>O<sub>3</sub>, NbO<sub>2</sub> and TT-Ta<sub>2</sub>O<sub>5</sub> which have been identified by powder X-ray diffraction. Upon reaction with H<sub>2</sub>S, the crystalline oxides afford layered sulfides of the form MS<sub>2</sub> (M = V, Nb and Ta), some of which exhibit behaviour typical of IF-like materials and have been characterised by HRTEM, powder X-ray diffraction and EDX analysis.</p> Chapter 7 outlines the experimental details for the synthesis, characterisation, reactions and compounds described in the preceding chapters. <p><strong>Chapter 8</strong> presents the characterising data for the new compounds described in chapters 2 and 3.</p> <p><strong>Appendix A</strong> contains details of the crystallographic data for the structurally characterised compound [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>PMe<sub>2</sub>}<sub>2</sub>].</sub></p></p> |
| spellingShingle | Molybdenum oxides Synthesis Derivatives Cyclopentadiene Clancy, G Clancy, Gerald Patrick Synthetic inorganic chemistry |
| title | Synthetic inorganic chemistry |
| title_full | Synthetic inorganic chemistry |
| title_fullStr | Synthetic inorganic chemistry |
| title_full_unstemmed | Synthetic inorganic chemistry |
| title_short | Synthetic inorganic chemistry |
| title_sort | synthetic inorganic chemistry |
| topic | Molybdenum oxides Synthesis Derivatives Cyclopentadiene |
| work_keys_str_mv | AT clancyg syntheticinorganicchemistry AT clancygeraldpatrick syntheticinorganicchemistry |